CN113385205B - Metal phosphide catalyst for heterogeneous hydroformylation reaction - Google Patents
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/18—Reducing with gases containing free hydrogen
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
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Abstract
The invention discloses an Rh-based multi-metal phosphide nano catalyst Rh 2‑x TM x P, the main active site of which is Rh site, forms inorganic phosphide together with other metals. The invention also discloses a preparation method of the Rh-based phosphide, which comprises the steps of mixing rhodium nitrate, transition metal nitrate and triphenylphosphine in ethanol and water solution, dripping the solution onto the surface of a carrier, and reducing at 550 ℃ to obtain the Rh-based phosphide catalyst. The invention also discloses application of the Rh-based phosphide catalyst in a styrene hydroformylation reaction. According to the invention, the electronic structure of the surface Rh atoms is regulated and controlled by doping other transition metals, so that the activity of the catalyst in the hydroformylation reaction is improved. Further optimizing the conditions of reaction temperature, pressure, etc., the proportion of 2-phenylpropionaldehyde to 3-phenylpropionaldehyde in the product can be controlled. The catalyst is a heterogeneous catalyst, is easier to separate and collect from a reaction system, and is suitable for industrial production.
Description
Technical Field
The invention relates to a metal phosphide catalyst for catalyzing heterogeneous hydroformylation reaction.
Background
Hydroformylation is an important class of chemical reactions with global yields exceeding 2000 tens of thousands of tons per year. The reactants of the hydroformylation reaction are unsaturated olefins and synthesis gas, and the product is an aldehyde with a higher economic added value. In addition, the aldehyde can be further reacted to prepare chemical products such as alcohol, amine, carboxylic acid, ester and the like, and the aldehyde can be widely applied to the fields of perfume, medicine and the like. The atom utilization rate of the hydroformylation reaction is 100%, meets the requirement of green development, can convert low-cost olefin into aldehyde, is used for producing fine chemicals, and meets the requirement of industrial upgrading. However, the current homogeneous catalysts widely used in industry are Rh and organic phosphine ligands, which are difficult to separate from solvents and products, and have the problems of noble metal loss, phosphorus-containing wastewater and the like. In addition, the price of the noble metal Rh has rapidly risen in recent years, so that the need for developing a highly efficient heterogeneous hydroformylation catalyst has been urgent.
Currently, the development of heterogeneous hydroformylation catalysts involves two ideas, respectively: (1) directly heterogenizing the mature homogeneous catalyst; (2) the inorganic auxiliary agent is used for regulating and controlling the electronic structure of Rh sites, thereby playing a role similar to that of homogeneous phosphine ligands. The preparation process of the catalyst is generally complex, and needs an oxygen-free environment, so that the cost is high; the latter catalysts have a low space-time yield and are difficult to meet industrial requirements. For example, patent CN111822045a discloses the use of ionic liquids to immobilize a homogeneous catalyst on SiO 2 Surface method, patent CN104710288A discloses a method of directly polymerizing an organic phosphine ligand to form an organic polymer backbone and supporting active metals, CN109876847B discloses a method of directly encapsulating a homogeneous catalyst in an S-1 molecular sieve. These methods all require the use of phosphine ligands, which are relatively complex to prepare and sensitive to air, and are extremely susceptible to oxidation in air. While CN109847741a and CN106362766a respectively disclose different supported monoatomic catalysts, this class of catalysts is free of phosphine ligand limitations, but the space-time yields are still low.
In conclusion, the development of the heterogeneous hydroformylation catalyst which does not contain phosphine ligand, has a simple preparation method and high activity has important significance and value.
Disclosure of Invention
In order to solve the defects and shortcomings of the existing heterogeneous hydroformylation reaction catalyst, the invention provides a novel inorganic metal phosphide catalyst without organic phosphine, which has higher activity in the hydroformylation reaction. The catalyst is a supported heterogeneous catalyst, so that the defect that the homogeneous catalyst is difficult to separate is avoided. The catalyst does not need an anaerobic environment in the preparation process, the preparation cost is low, the loading amount of noble metal Rh is moderate, and the used wet preparation process is mature and is easy to put into industrial application. The catalyst has high activity of unit site, and the whole space-time yield meets the industrial production requirement.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
rh-based inorganic metal phosphide catalyst 2-x TM x P represents one or a combination of Ti, mn, fe, co, ni, cu, zn, ga, zr, mo, ru, pd, ag, ir, pt, au transition metal TM and 0-2 x, wherein the active site of the catalyst can be only the surface Rh site, and can also comprise the Rh active site and the transition metal active site, wherein the Rh site provides main catalytic activity.
Preferably, the Rh metal loading is 0-10wt%, the mole ratio of the doped metal TM to Rh is x/(2-x), the mole ratio of the P element content to the total metal content is 1-3, and the rest is the carrier.
Preferably, the carrier is SiO 2 、Al 2 O 3 、CeO 2 、TiO 2 、ZrO 2 Oxide and one or a combination of ZSM-5, beta, Y, MCM, SAPO molecular sieves.
Preferably, x has a value of 0.1 to 1.
More preferably, x has a value of 0.2 to 0.4.
Alternatively, the heterogeneous hydroformylation reaction is a reaction of a heterogeneous olefin hydroformylation reaction to produce an aldehyde.
According to another aspect of the present invention, there is also provided a method for preparing a catalyst by impregnation reduction, comprising the steps of:
s1, uniformly mixing a rhodium source, transition metal salt and a phosphorus source in a solvent;
s2, dripping the mixed solution or the turbid liquid obtained in the step S1 into a carrier to obtain a catalyst precursor;
s3, drying the catalyst precursor obtained in the step S2, and reducing the catalyst precursor in a hydrogen atmosphere to obtain the supported metal phosphide solid catalyst.
Preferably, in the step of adding the mixed solution or the turbid liquid to the carrier, stirring is accompanied, followed by ultrasonic treatment.
Preferably, the rhodium source comprises any one or combination of rhodium trichloride, rhodium nitrate, triphenylphosphine carbonyl rhodium hydride, dicarbonyl rhodium acetylacetonate, and acetylacetonate carbonyl rhodium hydride.
Preferably, the transition metal salt is any one or a combination of metal chloride, nitrate and carbonate which need to be added.
Preferably, the phosphorus source is any one of phosphoric acid, monoammonium phosphate, diammonium phosphate, triphenylphosphine, 1, 2-bis-diphenylphosphine ethane, 1, 3-bis-diphenylphosphine propane, 1, 4-bis-diphenylphosphine butane, 1, 5-bis-diphenylphosphine pentane, 1, 6-bis-diphenylphosphine hexane, or a combination thereof.
Preferably, the solvent includes, but is not limited to, one of water, methanol, ethanol, benzene, toluene, xylene, acetone, chlorinated alkane, or a combination thereof.
Preferably, the carrier is SiO 2 、Al 2 O 3 、CeO 2 、TiO 2 、ZrO 2 And one or a combination of the oxides and ZSM-5 and Beta, Y, MCM, SAPO molecular sieves.
According to another aspect of the present invention, there is also provided a method for synthesizing an aldehyde using the supported metal phosphide solid catalyst, characterized by comprising: in CO/H 2 In the mixed atmosphere, the mixed system containing unsaturated olefin and the supported metal phosphide solid catalyst is subjected to hydroformylation reaction at 40-120 ℃ to obtain the corresponding aldehyde.
Preferably, the condition of the hydroformylation reaction is controlled at a reaction temperature of 40-60 ℃, H 2 The total pressure of the CO synthesis gas is 3-10 MPa, more preferably, the temperature is 40-50 ℃ and the pressure is 5-8 MPa, so as to improve the selectivity of the isomeric aldehyde product.
Preferably, the conditions of the hydroformylation reaction are controlled at a reaction temperature of 100-140 ℃ and H 2 The total pressure of the CO synthesis gas is 0.1-3 MPa, more preferably, the temperature is 100-120 ℃ and the pressure is 0.5-2 MPa, so as to improve the selectivity of normal aldehyde products.
Preferably, the unsaturated olefin comprises any one of styrene, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene.
Preferably, said H 2 The ratio of the synthesis gas to CO is 0.5 to 3, more preferably 0.8 to 1.2.
The activity test method of the catalyst comprises the following steps:
adding olefin and catalyst into organic solvent, and charging CO and H 2 Is reacted under stirring at 800 rpm. The reaction temperature is 40-140 ℃, the reaction pressure is 0.1-10 MPa, H 2 The ratio of the CO synthesis gas is 0.5-3, and the mol ratio of the unsaturated olefin to rhodium is 100:1-10000:1.
The invention has the beneficial effects that:
1. represented by Rh 2-x TM x The Rh-based metal inorganic phosphide of P is used as a supported metal phosphide solid catalyst for heterogeneous hydroformylation reaction, so that the heterogeneous hydroformylation reaction has moderate load and high space-time yield;
2. the preparation process of the catalyst is simple, no oxygen-free environment is needed, and the reduction temperature is moderate;
3. in the reaction process of synthesizing aldehyde by using the catalyst, the catalyst and reactants are easy to separate, and no phosphorus-containing wastewater is generated.
Detailed Description
The foregoing and other objects of the invention will be apparent from the following more particular description of preferred embodiments of the invention, as illustrated in the accompanying drawings. The following examples are for illustration only and should not be construed as limiting the scope of the invention. The Rh loading of the catalysts in both the comparative example and the example was 1wt%.
1. Process for preparing catalyst
Comparative example 1
The catalyst is loaded on SiO 2 The preparation method of the surface Rh nano-particles comprises the following steps: rhodium nitrate is dissolved in ethanol and water solution and is immersed in SiO 2 And calcining the surface at 450 ℃ and reducing at 550 ℃ to obtain the Rh metal nano-particles. The loading of Rh was 1wt%.
Comparative example 2
The catalyst is loaded on SiO 2 Surface Rh 2 The preparation method of the P nano-particles comprises the following steps: dissolving rhodium nitrate and triphenylphosphine in ethanol and water solution, soaking in SiO 2 Surface, through 550Reducing at a temperature of Rh to obtain Rh 2 The P nano particles are characterized by X-ray diffraction and a transmission electron microscope, and the structure of the P nano particles is proved to be Rh 2 P. The loading of Rh was 1wt% and the Rh/P molar ratio in the precursor was 2:1.
Example 1
Rhodium nitrate, cobalt nitrate and triphenylphosphine were first mixed in ethanol and water to give a substantially homogeneous liquid. The liquid is uniformly impregnated into SiO 2 On the support, reduction was carried out by a temperature programmed method (in this example, H was used 2 Reduction at 550 c). Characterization of the prepared catalyst by X-ray diffraction and transmission electron microscope proves that the active site structure and Rh of the catalyst are 2 P is similar and is an inverse fluorite structure. Wherein the loading of Rh was controlled to 1wt%, rh: co: P=7:1:4 (mol), i.e., the molar ratio of the total metal content to the amount of phosphorus added was controlled to 2:1.
2. Comparison of the Performance of different catalysts in the reaction for the Synthesis of aldehydes
(1) Comparison of the reactivity of different catalysts
In all catalyst reaction evaluation examples and comparative examples, the performance of the hydroformylation reaction of styrene was evaluated using a batch process, a reaction vessel filled with 30mL of toluene solvent, an appropriate amount of styrene and catalyst was sealed, synthesis gas at a corresponding pressure was charged, placed in a constant temperature oil bath, a small amount of solution was taken out after an interval of time, and the corresponding composition was measured by gas chromatography GC. Table 1 shows the performance of some catalysts prepared as described above in actual reactions.
Comparative example 3
Using simple Rh nanoparticles, 45.6% of styrene can be converted in 4h under the reaction condition, the selectivity of the hydroformylation product (2-phenylpropionaldehyde or 3-phenylpropionaldehyde) in the product is 98.7%, and the ratio of normal isomer aldehyde is 46:54. Since Rh/SiO is 2 The catalyst activity was low, and the comparative example used styrene/Rh addition=1794 mol/mol, the catalyst addition being 2 times that of examples 2 to 14.
Comparative example 4
In comparative example 4, the inorganic phosphorus doped Rh is used as a catalyst, the reactivity is improved to a certain extent, the conversion rate of 4h is improved to 64.7% compared with that of comparative example 1, and the hydroformylation selectivity and the normal isomeric aldehyde ratio are basically unchanged.
Example 2
Example 2 based on comparative example 4, the catalyst was further doped with a transition metal Co, and the conversion of 4h was further increased to 86.8% using a rho bi-metal phosphide as the catalyst, while the hydroformylation selectivity and the n-isomer aldehyde ratio were substantially unchanged.
Example 3
Example 3 the doping amount of transition metal Co was increased on the basis of example 2, and the preparation method was similar to example 1, only changing the addition amount of cobalt nitrate. The 4h conversion was further increased to 89.8% with substantially unchanged hydroformylation selectivity and n-isomer aldehyde ratio. The rate of conversion product per unit site per unit Time (TOF) of this catalyst is in excess of 2500h -1 The mass (STY) of the conversion product per unit mass of the catalyst (containing the mass of the carrier) was 33.4g Product(s) /(g Catalyst H) and the hydroformylation product selectivity is as high as 99.8%. 0.03% Rh under similar reaction conditions 1 TOF of the/ZnO-nw catalyst (Angew. Chem. Int. Ed.2016,55, 16054-16058) was 3167h -1 Slightly higher than in this example, but with lower active site loading, and therefore lower STY, only 1.24g Product(s) /(g Catalyst H) and no selectivity in the product for linear and branched aldehydes is essentially 1:1.
Example 4
Example 4 the doping amount of transition metal Co was further increased on the basis of example 3, and the preparation method was similar to example 1, only changing the addition amount of cobalt nitrate. The conversion for 4h is reduced to 83.3% instead, while the hydroformylation selectivity and the n-isomer aldehyde ratio are substantially unchanged.
Example 5
Example 5 the doping amount of transition metal Co was further increased on the basis of example 4, and the preparation method was similar to example 1, only changing the addition amount of cobalt nitrate. The 4h conversion was further reduced to 50.0% with substantially unchanged hydroformylation selectivity and normal isomeric aldehyde ratio.
Example 6
Example 6 the doped metal of example 3 was changed from Co to Pd in a similar manner to example 3, with only cobalt nitrate replaced with palladium nitrate. The 4h conversion became 93.8% while the hydroformylation selectivity and the n-isomer aldehyde ratio were essentially unchanged.
Example 7
Example 7 the doped metal of example 3 was changed from Co to Ni in a similar manner to example 3 with only cobalt nitrate replaced with nickel nitrate. The 4h conversion became 96.2% while the hydroformylation selectivity and the n-isomer aldehyde ratio were essentially unchanged.
Example 8
Example 8 the doped metal of example 3 was changed from Co to Ru in a similar manner to example 3 with only cobalt nitrate replaced with ruthenium nitrate. The 4h conversion became 53.6% while the hydroformylation selectivity and the n-isomer aldehyde ratio were essentially unchanged.
TABLE 1 comparison of different Rh phosphide catalysts and Rh catalyst Performance
Reaction conditions: styrene/Rh addition = 3588mol/mol, reaction temperature 80 ℃, synthesis pressure 3MPa, CO/H 2 ＝1:1； a Due to Rh/SiO 2 The catalyst activity was lower, the comparative example used styrene/Rh addition = 1794mol/mol, the remaining conditions being the same;
(2) Comparison of reactivity under different reaction conditions
Examples 9 to 14 are used to compare the reactivity of different reaction conditions in the preparation of aldehydes using the bimetallic supported phosphide solid catalyst of the present invention, and the catalyst used was the same as that in example 6, i.e., rh was used 7 Pd 1 P 4 /SiO 2 A catalyst.
Example 9
The reaction conditions for example 9 were the same as in example 6, i.e., the reaction temperature was 80℃and the total synthesis gas pressure was 3MPa, corresponding to a 4h conversion of 93.8%, at which time the ratio of 3-phenylpropionaldehyde to 2-phenylpropionaldehyde in the product was 48:52.
Example 10
Example 10 reduced the reaction temperature to 70℃with respect to example 9, a conversion of 90.7% for 6 hours and a normal isomer aldehyde ratio of 39:61. That is, it is stated that lowering the temperature reduces the activity of the hydroformylation reaction, but increases the 2-phenylpropionaldehyde fraction in the product, without changing the pressure.
Example 11
Example 11 the reaction temperature was further reduced to 60℃on the basis of example 10, the conversion of 10h was 91.4% and the n-isomer aldehyde ratio was 27:73.
Example 12
Example 12 on the basis of example 11, the synthesis gas pressure was increased to 4mpa without changing the temperature, the conversion of 11h was 96.2% and the n-isomer aldehyde ratio was 17:83. That is, under the condition of constant temperature, the pressure is increased to slightly increase the activity of the catalyst, and the selectivity of the 2-phenylpropionaldehyde in the product is further improved.
Example 13
Example 13 based on example 12, further temperature and pressure were reduced, the reaction conditions were 40 ℃, 6MPa, and after 45 hours of reaction, the conversion rate reached 98.6%, at which time the n-isomer aldehyde ratio was 5:95.
Example 14
Example 14 on the basis of example 9, the reaction temperature was increased, the synthesis gas pressure was reduced, the reaction conditions were 120 ℃, 2MPa, the conversion rate reached 90.0% in 3h, and the n-isomer aldehyde ratio in the product was 62:38. This means that the selectivity of 3-phenylpropionaldehyde can be improved by increasing the reaction temperature and decreasing the reaction pressure.
TABLE 2 catalyst reactivity under different temperature and pressure conditions
Examples 9-14 other reaction conditions: styrene/Rh addition = 3588mol/mol, CO/H 2 ＝1:1。
As can be seen from Table 2, the temperature and pressure are high (40-60 ℃ C., H 2 The total pressure of the CO synthesis gas is 3-10 MPa, which is favorable for the generation of 2-phenylpropionaldehyde, and the high temperature and the low pressure (100-140 ℃ and H) 2 The total pressure of the CO synthesis gas is 0.1-3 MPa), which is favorable for the generation of 3-phenylpropionaldehyde. Compared to the most common reaction conditions (80 ℃, H 2 The total CO synthesis gas pressure 3 MPa), example 12 increases the selectivity of 2-phenylpropionaldehyde to more than 95%, although the STY is reduced to 1.15g Product(s) /(g Catalyst H), but still substantially meet the industrial production requirements.
Claims (8)
1. A supported metal phosphide solid catalyst for heterogeneous hydroformylation reaction comprises rhodium Rh, transition metal TM and phosphorus P, and is characterized in that: the main active site of the catalyst is rhodium Rh, the TM is Co, ni or Pd, and the catalyst is Rh 7.5 Co 0.5 P 4 、Rh 7 Co 1 P 4 、Rh 6 Co 2 P 4 、Rh 7 Pd 1 P 4 、Rh 7 Ni 1 P 4 Rh, TM and P form metal phosphide and are loaded on the carrier, the loading amount of Rh metal is 0-1 wt%, and the loading amount is not equal to zero.
2. The supported metal phosphide solid catalyst according to claim 1, wherein the carrier is SiO 2 、Al 2 O 3 、CeO 2 、TiO 2 、ZrO 2 Oxide and one or a combination of ZSM-5, beta, Y, MCM, SAPO molecular sieves.
3. The supported metal phosphide solid catalyst according to claim 1, wherein the heterogeneous hydroformylation is a heterogeneous olefin hydroformylation reaction to form aldehydes.
4. A supported metal phosphide solid catalyst Rh as claimed in any one of claims 1 to 3 7.5 Co 0.5 P 4 、Rh 7 Co 1 P 4 、Rh 6 Co 2 P 4 、Rh 7 Pd 1 P 4 Or Rh 7 Ni 1 P 4 Is characterized in that the preparation method comprises the following steps:
s1, uniformly mixing a rhodium source, transition metal salt Co, ni or Pd and a phosphorus source in a solvent;
s2, dripping the mixed solution or the turbid liquid obtained in the step S1 into a carrier to obtain a catalyst precursor;
s3, drying the catalyst precursor obtained in the step S2, and reducing the catalyst precursor in a hydrogen atmosphere to obtain the supported metal phosphide solid catalyst, wherein the Rh metal loading amount is 0-1 wt%.
5. The method according to claim 4, wherein the rhodium source comprises any one of rhodium trichloride, rhodium nitrate, triphenylphosphine carbonyl rhodium hydride, dicarbonyl acetylacetonate rhodium, acetylacetonate carbonyl rhodium hydride, or a combination thereof;
and/or the transition metal salt is any one or combination of metal chloride, nitrate and carbonate which need to be added;
and/or the phosphorus source is phosphoric acid, monoammonium phosphate, diammonium phosphate, triphenylphosphine, 1, 2-bis-diphenylphosphine ethane, 1, 3-bis-diphenylphosphine propane, 1, 4-bis-diphenylphosphine butane, 1, 5-bis-diphenylphosphine pentane,
Any one or combination of 1, 6-bis-diphenylphosphine hexane;
and/or the solvent is a combination of one or more polar solvents and a non-polar solvent;
and/or the carrier is one or a combination of oxide and molecular sieve, the oxide is selected from SiO 2 、Al 2 O 3 、CeO 2 、TiO 2 、ZrO 2 The molecular sieve is selected from ZSM-5 and Beta, Y, MCM, SAPO.
6. A method for synthesizing an aldehyde using the supported metal phosphide solid catalyst as set forth in any one of claims 1 to 3, characterized in that:
in CO/H 2 In the mixed atmosphere, the mixed system containing unsaturated olefin and the supported metal phosphide solid catalyst is subjected to hydroformylation reaction at 40-120 ℃ to obtain the corresponding aldehyde.
7. The process according to claim 6, wherein the hydroformylation reaction is carried out at a reaction temperature of 40 to 60℃and H 2 The total pressure of the CO synthesis gas is 3-10 MPa;
or the reaction temperature is 100-140 ℃ and H 2 The total pressure of the CO synthesis gas is 0.1-3 MPa.
8. The method of claim 6, wherein H 2 The ratio of the/CO synthesis gas is 0.5-3.
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